Sulphamic acid fluorides



Patented Sept. 13, 1938 UNITED STATES PATENT OFFlCE SULPHAMIC ACID FLUORIDES Gerhard Schrader and Otto Bayer, Leverknsen- I. G. Werk, Germany, aasignors to Winthrop Chemical Company, Inc., New York, N. Y., a corporation of New York No Drawing. Application May 25, 1936, Serial No. 81,771. In Germany May 14, 1935 8 Claims. (Cl. 260-543) This invention relates to new and valuable The reaction is performed in the presence of sulphamic acid fluorides and to a process for a solvent for one or both reaction components. preparing the same. Water has proved to be particularly advanta- In accordance with the present invention geous. Preferably the reaction is carried out at sulphamic acid fluorides of the general formula elevated temperatures, for instance, at IO-100 C. 6

R It is surprising that the above defined sulphso F amic acid fluorides can be obtained in accordance with the process of the present inven- R, tion since the sulphamic acid chlorides used as 10 in which R1 and R: stand for saturated aliphatic Starting materials are Saponified y Water at 10 radicals a carbon atom of which is directly conelevated t pe at snected with the nitrogen atom which aliphatic The a v d fin d su p ami d flu d s a radicals may be linked together so t they stable to water even on heating. They are solform a. cycloaliphatic ring system, can be obin benzene. benzine, ether. methyl alcohol. tamed by reacting upon sulphamic acid chlorldes ethyl alcohol, acetone, glycols, and acetic acid 15 f the general formula esters. The lower members in which R1 and R2 R stand for all yl radicals containing from 1-3 carbon atoms as, for example, the dimethyl and diethyl sulphamic acid fluorides are water-white R, easily mobile liquids of a characteristic chloro- 20 in which R1 and R: have the same meaning as form-like Odom The sulphamic acid Quorides in the first formula with soluble metallic fluorides mt etch glass- Due stabillty they in the presence of a solvent or a liquid diluent are suitable as intermediate products for dye- RI and R2 may stand for instance for the stufls. They have proved especially advantamethyl, ethyl, propyl, hexyl and dodecyl radical. for the Purpose of combating Parasltes R1 and R2 may also denote alkyl radicals which Partlculafly P insectslower members of are substituted, for instance, by halogen atoms the sulphamlc acid fluondes which R1 and R2 or the amino, cyano,mercapto,alkoxy,carboxylic stand for alkyl radicals continuing iron} acid, carboxylic acid ester, sulfonic acid or aryl carbqn atoms have proved to most slut-able groun since they maybe easily vaporized or nebulized. 80

Rd and R2 may be linked together so that they The sulphamlq acid fluorldes may be employed form a cycloaliphatic ring system as it is, for i the most varied manner- They may used instance, the case in the piperidyl radical or the m the gaseous Phase either a1ne w1th the morphonnyl radicaL addition of other inert gases or gases being effec- As starting sulphamic acid chlorides there tive for combating vermin, for instance, carbon come, for instance, into consideration the didioxlde carbon monoxide, f f qxlde methylsulphamic acid chloride, the diethylsulpm drocyanic acid. Also warning or irritating subamic acid chloride, the methybethyhsulpm stances, such as chloroforrnic acid ester may be me acid chloride, methyl propybsulpm added to the sulphamic acid fluorides to be gasi- 40 amic acid chloride, the methyl hexyl sulphamic 40 acid chloride, the ethyl dodecyl sulphamic acid Furthermwe, they a be P 9 nebuchloride, the methylmercaptoethyl methy1 m lized in the form of their solutions, for instance, amic acid chloride, the phenyl ethybmethyl in water or low boillngsolvents, such as carbon slflphamic acid chloride, the pfidmhlomdiethyl tetrachloride, acetone, benzene, benzine, or also sulphamic acid chloride, the 1 1 1- in admixture with unsaturated solvents, as are sulphamic acid chlorlde as well as t sulphamic obtained for instance in the petroleum fractionacid cmorides 1 pipefldjne morpholine monoation. To solutions or dispersions of the said methylamino acetic acid or its methyl ester kind likewise other media for combating vermin,

h aid sulphamic a id chl rid for for instance, nicotin may be added. The soluinstance, be obtained by the action of sulphuryl tions of the sulpha c d flu y 8-150 50 chloride on the respective secondary bases. be absorbed by a e ubstances, for instance As metallic fluorides particularly the waterpaper or porous substances and may then be soluble metallic fluorides, for instance the potasemployed. sium, sodium, ammonium, zinc and silver fluo- The sulphamic acid fluorides may also be used rides have proved to be advantageous. in solid or paste-like form alone or in admix- 55 ture with inert substances and/or other solid or liquid media' for combatting vermin. Talc or chalk may, for instance, serve as inert stretching agent. The sulphamic acid fluorides may be marketed in the form 01' powder or in the form of tablets.

The sulphamic acidfluorides may serve 'for combating the most varied kinds of vermin. They have proved to be especially suitable for combating Calandra aranaria, Tenebrio' molitor and others, bedbugs, cockroaches, lice, flies, gnats, all kinds of moths, fur-beetle, carpet-beetle and its larva, ants, plant-lice, Phylloxera, shield-lice and others. The sulphamic acid fluorides may also be employed for exterminating rats, mice and the like. p

The following examples illustrate the invention, the parts being by weight:

Example 1 I 143.5 parts of dimethyl sulphamic acid chloride (B. P. under 10 mm. '72-'13" C.) are refluxed for 2-3 hours at 90-100 C. with an aqueous solution of 100 parts of potassium fluoride in 120 parts of water while stirring. After the potassium chloride separated has been dissolved by the addition of water, the oily reaction product is extracted with ether. The ethereal solution is deacidifled with solid potassium carbonate and dried with the aid of sodium sulfate. After the ether is distilled off the dimethyl sulphamic acid fluoride remains as an oily liquid. By a single distillation in vacuum (13. P. under 14 mm. 42-43 C.) the crude product is obtained as an oil which is water-white easily mobile, and of a sweetish chloroform-like odour. By this method of work ing, -85 parts of pure fluoride are obtained.

Instead of potassium fluoride, with the same success, also sodium fluoride or zinc fluoride may be employed. When using solid sulphamic acid chlorides it is useful to dissolve the same in an indifferent dissolving agent, as for example xylene, and then to bring them into reaction with the aqueous solution of alkali fluoride.

Example 2 171.5 parts of diethylsulphamic acid chloride are refluxed for 3-4 hours at -l00 C. with an aqueous solution of parts of potassium fluoride in parts of water while stirring well. After working up in the manner described in Example l, a nearly colorless crude product is obtained, which is obtained pure by a single distillation (B. P. under 12 mm. 67 C.) The sulphamic acid fluoride obtained in a good yield (90- 100' parts) has a very strong chloroform-like, phenolic odour.

with the same good yields the sulphamic acid chlorides of the following bases can be converted into the respective sulphamic acid fluorides:

CHrCHrNH-CH:

We claim:- lll. sulphamic acid fluorides of the general form a in which R1 and R: stand for saturated aliphatic radicals containing from 1-3 carbon atoms a carbon atom of which is directly connected with the nitrogen atom, which compounds are stable to water even on heating, which are further soluble in benzene, benzine, ether, methyl alcohol, ethyl alcohol, acetone, glycols and acetic acid esters, and represent water-white liquids of a characteristic chloroform-like odour and which do not etch glass.

3. The process for preparing sulphamic acid fluorides which comprises reacting upon sulphamic acid chlorides of the general formula N-BOaCl in which R1 and R: stand for saturated aliphatic radicals a carbon atom of which is directly connected with the nitrogen atom with water-soluble metallic fluorides in the presence of water.

:i sulphamic acid fluorides of the general form a in which R1 and R2 stand for saturated aliphatic radicals, which compounds are stable to water even on heating, which are further soluble in benzene, benzine, ether, methyl alcohol, ethyl alcohol, acetone, glycols and acetic acid esters and which do not etch glass.

5. sulphamic acid fluorides selected from the group consisting of piperidyl and morpholinyl sulphamic acid fluorides, which compounds are stable to water even on heating, which are further soluble in benzene, benzine, ether, methyl alcohol, ethyl alcohol, acetone, glycols and acetic acid esters and which do not etch glass.

6. The process for preparing sulphamic acid fluorides which comprises reacting upon sulphamic acid chlorides of the general formula:

in which R1 and R: stand for saturated aliphatic radicals with water-soluble metallic fluorides in the presence of water.

7. The process of preparing sulphamic acid fluorides which comprises reacting upon sulphamic acid chlorides selected from the group con- 'sisting of morpholinyl and piperidyl sulphamic acid chlorides with water-soluble metallic fluorides in the presence of water.

8. Sulphamic acid fluorides of the group consisting of compounds of the general formula N-SOzF wherein R1 and R2 stand for saturated aliphatic radicals a carbon atom of each being directly connected with the nitrogen atom and compounds of that general formula wherein R1 and R2 together form a divalent saturated aliphatic chain linked by carbon atoms with the N, thereby forming a ring system, which compounds are stable to water even on heating, which are further soluble in benzene, benzine, ether, methyl alcohol, ethyl alcohol, acetone, glycols and acetic acid esters and which do not etch glass. 

